Selected ion flow tube study of the reactions of H3O+ and NO+ with a series of primary alcohols in the presence of water vapour in support of selected ion flow tube mass spectrometry

Španěl, Patrik; Žabka, Ján; Zymak, Illia; Smith, David

doi:10.1002/rcm.7811

Cited by 16 publications

(24 citation statements)

References 33 publications

(43 reference statements)

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“…At m/z 79.075, another association ion was observed to interfere with benzene. This peak was assigned to the [C 3 H 7 OH]H 3 O + ion, which is attributed to hydrated propanols 99 . These interferences have a big impact in the analysis of benzene in process gases like biogases and can obscure quantitative assessments, because such gases are typically rich in acetic acid, sulfur compounds, and propanols and additionally are saturated with water vapor, 1 which would favor the formation of association clusters.…”

Section: Resultsmentioning

confidence: 99%

Determination of trace compounds and artifacts in nitrogen background measurements by proton transfer reaction time‐of‐flight mass spectrometry under dry and humid conditions

et al. 2021

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A qualitative analysis was applied for the determination of trace compounds at the parts per trillion in volume (ppt v ) level in the mass spectra of nitrogen of different qualities (5.0 and 6.0) under dry and humid conditions. This qualitative analysis enabled the classification and discovery of hundreds of new ions (e.g., [S x ]H + species) and artifacts such as parasitic ions and memory effects and their differentiation from real gas impurities. With this analysis, the humidity dependency of all kind of ions in the mass spectrum was determined. Apart from the inorganic artifacts previously discovered, many new organic ions were assigned as instrumental artifacts and new isobaric interferences could be elucidated. From 1140 peaks found in the mass range m/z 0-800, only 660 could be analyzed due to sufficient intensity, from which 463 corresponded to compounds. The number of peaks in nitrogen proton transfer reaction (PTR) spectra was similarly dominated by nonmetallic oxygenated organic compounds (23.5%) and hydrocarbons (24.1%) Regarding only gas impurities, hydrocarbons were the main compound class (50.2%). The highest contribution to the total ion signal for unfiltered nitrogen under dry and humid conditions was from nonmetallic oxygenated compounds. Under dry conditions, nitrogen-containing compounds exhibit the second highest contribution of 89% and 96% for nitrogen 5.0 and 6.0, respectively, whereas under humid conditions, hydrocarbons become the second dominant group with 69% and 86% for nitrogen 5.0 and 6.0, respectively. With the gathered information, a database can be built as a tool for the elucidation of instrumental and intrinsic gas matrix artifacts in PTR mass spectra and, especially in cases, where dilution with inert gases plays a significant role. K E Y W O R D Sgas impurities, gas traces, industrial gases, proton transfer reaction time-of-flight mass spectrometry, volatile organic compounds

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Section: Resultsmentioning

confidence: 99%

Determination of trace compounds and artifacts in nitrogen background measurements by proton transfer reaction time‐of‐flight mass spectrometry under dry and humid conditions

et al. 2021

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“…As a CI‐based analytical technique, the relevant ion chemistry associated with the reaction of volatile compounds with the reagent ions is vital to the accurate identification and quantification of trace gases using SIFT‐MS. Several product ion distribution studies have been reported on CI using H 3 O + , NO + , and O 2 + precursor ions for a range of applications and for a wide variety of organic compounds including alcohols, aldehydes and ketones, carboxylic acids, esters, indoles, N‐ and O‐containing heterocyclic compounds, organosulfur and organoselenium, oxygenated biogenic/non‐methane volatile organic compounds, terpenes and terpenoids, siloxanes, and other compounds with biological applications …”

Section: Resultsmentioning

confidence: 99%

Gas‐phase chemical ionization of 4‐alkyl branched‐chain carboxylic acids and 3‐methylindole using H₃O⁺, NO⁺, and O₂⁺ ions

Castada

Barringer

Wick

2017

Rapid Comm Mass Spectrometry

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“…What we have learned so far is that the dominant ion‐molecule reaction process involved is ligand switching of analyte molecules, A, with H 2 O ligands in the reagent H 3 O + (H 2 O) n cluster ions. This is most likely if A is a polar molecule, as many SIFT experiments have shown, 35,36 when analyte ions AH + (H 2 O) n ‐1 result. The often‐assumed proton transfer from the reagent cluster ions to A molecules forming AH + ions will, in most cases, be endothermic, and can rarely occur.…”

Section: Discussionmentioning

confidence: 99%

Reagent and analyte ion hydrates in secondary electrospray ionization mass spectrometry (SESI‐MS), their equilibrium distributions and dehydration in an ion transfer capillary: Modelling and experiments

Dryahina

Som

Smith

et al. 2021

Rapid Comm Mass Spectrometry

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Rationale Secondary electrospray ionization (SESI) in a water spray environment at atmospheric pressure involves the reactions of hydrated hydronium reagent ions, H3O+(H2O)n, with trace analyte compounds in air samples. Understanding the formation and dehydration of reagent and analyte ions is the foundation for meaningful quantification of trace compounds by SESI‐mass spectrometry (MS). Methods A numerical model based on gas‐phase ion thermochemistry is developed that describes equilibria in H3O+(H2O)n reagent cluster ion distributions and ligand switching reactions with polar NH3 molecules leading to equilibrated hydrated ammonium ions NH4+(H2O)m. The model predictions are compared with experimental results obtained using a cylindrical SESI source coupled to an ion‐trap mass spectrometer via a heated ion transfer capillary. Non‐polar isoprene, C5H8, was used to further probe the nature of the reagent ions. Results Equilibrium distributions of H3O+(H2O)n ions and their reactions with NH3 molecules have been characterized by the model in the near‐atmospheric pressure SESI source. NH3 analyte molecules displace H2O ligands from the H3O+(H2O)n ions at the collisional rate forming NH4+(H2O)m ions, which travel through the heated ion transfer capillary losing H2O molecules. The data for variable NH3 concentrations match the model predictions and the C5H8 test substantiates the notion of dehydration in the heated capillary. Conclusions Large cluster ions formed in the SESI region are dehydrated to H3O+(H2O)1,2,3 and NH4+(H2O)1,2 while passing through the heated capillary, and considerable diffusion losses also occur. This phenomenon is also predicted for other polar analyte molecules, A, that can undergo similar switching reactions, thus forming AH+ and AH+(H2O)m analyte ions.

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Selected ion flow tube study of the reactions of H₃O⁺ and NO⁺ with a series of primary alcohols in the presence of water vapour in support of selected ion flow tube mass spectrometry

Cited by 16 publications

References 33 publications

Determination of trace compounds and artifacts in nitrogen background measurements by proton transfer reaction time‐of‐flight mass spectrometry under dry and humid conditions

Determination of trace compounds and artifacts in nitrogen background measurements by proton transfer reaction time‐of‐flight mass spectrometry under dry and humid conditions

Gas‐phase chemical ionization of 4‐alkyl branched‐chain carboxylic acids and 3‐methylindole using H₃O⁺, NO⁺, and O₂⁺ ions

Reagent and analyte ion hydrates in secondary electrospray ionization mass spectrometry (SESI‐MS), their equilibrium distributions and dehydration in an ion transfer capillary: Modelling and experiments

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Selected ion flow tube study of the reactions of H3O+ and NO+ with a series of primary alcohols in the presence of water vapour in support of selected ion flow tube mass spectrometry

Cited by 16 publications

References 33 publications

Determination of trace compounds and artifacts in nitrogen background measurements by proton transfer reaction time‐of‐flight mass spectrometry under dry and humid conditions

Determination of trace compounds and artifacts in nitrogen background measurements by proton transfer reaction time‐of‐flight mass spectrometry under dry and humid conditions

Gas‐phase chemical ionization of 4‐alkyl branched‐chain carboxylic acids and 3‐methylindole using H3O+, NO+, and O2+ ions

Reagent and analyte ion hydrates in secondary electrospray ionization mass spectrometry (SESI‐MS), their equilibrium distributions and dehydration in an ion transfer capillary: Modelling and experiments

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Selected ion flow tube study of the reactions of H₃O⁺ and NO⁺ with a series of primary alcohols in the presence of water vapour in support of selected ion flow tube mass spectrometry

Gas‐phase chemical ionization of 4‐alkyl branched‐chain carboxylic acids and 3‐methylindole using H₃O⁺, NO⁺, and O₂⁺ ions